Organometal catalyst compositions

ABSTRACT

This invention provides catalyst compositions that are useful for polymerizing at least one monomer to produce a polymer. This invention also provides catalyst compositions that are useful for polymerizing at least one monomer to produce a polymer, wherein said catalyst composition comprises a post-contacted organometal compound, a post-contacted organoaluminum compound, and a post-contacted fluorided silica-alumina.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional application of U.S. patent applicationSer. No. 10/037,016 filed Dec. 21, 2001 now U.S. Pat. No. 6,613,852,which is a divisional application of U.S. patent application Ser. No.09/401,354, now U.S. Pat. No. 6,355,594 B1, both of which areincorporated herein in their entirety by reference.

FIELD OF THE INVENTION

This invention is related to the field of organometal catalystcompositions.

BACKGROUND OF THE INVENTION

The production of polymers is a multi-billion dollar business. Thisbusiness produces billions of pounds of polymers each year. Millions ofdollars have been spent on developing technologies that can add value tothis business.

One of these technologies is called metallocene catalyst technology.Metallocene catalysts have been known since about 1960. However, theirlow productivity did not allow them to be commercialized. About 1975, itwas discovered that contacting one part water with one parttrimethylaluminum to form methyl aluminoxane, and then contacting suchmethyl aluminoxane with a metallocene compound, formed a metallocenecatalyst that had greater activity. However, it was soon realized thatlarge amounts of expensive methyl aluminoxane were needed to form anactive metallocene catalyst. This has been a significant impediment tothe commercialization of metallocene catalysts.

Borate compounds have been used in place of large amounts of methylaluminoxane. However, this is not satisfactory, since borate compoundsare very sensitive to poisons and decomposition, and can also be veryexpensive.

It should also be noted that having a heterogeneous catalyst isimportant. This is because heterogeneous catalysts are required for mostmodern commercial polymerization processes. Furthermore, heterogeneouscatalysts can lead to the formation of substantially uniform polymerparticles that have a high bulk density. These types of substantiallyuniform particles are desirable because they improve the efficiency ofpolymer production and transportation. Efforts have been made to produceheterogeneous metallocene catalysts; however, these catalysts have notbeen entirely satisfactory.

Therefore, the inventors provide this invention to help solve theseproblems.

SUMMARY OF THE INVENTION

An object of this invention is to provide a process that produces acatalyst composition that can be used to polymerize at least one monomerto produce a polymer.

Another object of this invention is to provide the catalyst composition.

Another object of this invention is to provide a process comprisingcontacting at least one monomer and the catalyst composition underpolymerization conditions to produce the polymer.

Another object of this invention is to provide an article that comprisesthe polymer produced with the catalyst composition of this invention.

In accordance with one embodiment of this invention, a process toproduce a catalyst composition is provided. The process comprises (oroptionally, “consists essentially of”, or “consists of”) contacting anorganometal compound, an organoaluminum compound, and a fluoridedsilica-alumina to produce the catalyst composition,

wherein said organometal compound has the following general formula:(X¹)(X²)(X³)(X⁴)M¹

wherein M¹ is selected from the group consisting of titanium, zirconium,and hafnium;

wherein (X¹) is independently selected from the group consisting ofcyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls,substituted indenyls, and substituted fluorenyls;

wherein substituents on the substituted cyclopentadienyls, substitutedindenyls, and substituted fluorenyls of (X¹) are selected from the groupconsisting of aliphatic groups, cyclic groups, combinations of aliphaticand cyclic groups, silyl groups, alkyl halide groups, halides,organometallic groups, phosphorus groups, nitrogen groups, silicon,phosphorus, boron, germanium, and hydrogen;

wherein at least one substituent on (X¹) can be a bridging group whichconnects (X¹) and (X²);

wherein (X³) and (X⁴) are independently selected from the groupconsisting of halides, aliphatic groups, substituted aliphatic groups,cyclic groups, substituted cyclic groups, combinations of aliphaticgroups and cyclic groups, combinations of substituted aliphatic groupsand cyclic groups, combinations of aliphatic groups and substitutedcyclic groups, combinations of substituted aliphatic groups andsubstituted cyclic groups, amido groups, substituted amido groups,phosphido groups, substituted phosphido groups, alkyloxide groups,substituted alkyloxide groups, aryloxide groups, substituted aryloxidegroups, organometallic groups, and substituted organometallic groups;

wherein (X²) is selected from the group consisting of cyclopentadienyls,indenyls, fluorenyls, substituted cyclopentadienyls, substitutedindenyls, substituted fluorenyls, halides, aliphatic groups, substitutedaliphatic groups, cyclic groups, substituted cyclic groups, combinationsof aliphatic groups and cyclic groups, combinations of substitutedaliphatic groups and cyclic groups, combinations of aliphatic groups andsubstituted cyclic groups, combinations of substituted aliphatic groupsand substituted cyclic groups, amido groups, substituted amido groups,phosphido groups, substituted phosphido groups, alkyloxide groups,substituted alkyloxide groups, aryloxide groups, substituted aryloxidegroups, organometallic groups, and substituted organometallic groups;

wherein substituents on (X²) are selected from the group consisting ofaliphatic groups, cyclic groups, combinations of aliphatic groups andcyclic groups, silyl groups, alkyl halide groups, halides,organometallic groups, phosphorus groups, nitrogen groups, silicon,phosphorus, boron, germanium, and hydrogen;

wherein at least one substituent on (X²) can be a bridging group whichconnects (X¹) and (X²);

wherein the organoaluminum compound has the following general formula:Al(X⁵)_(n)(X⁶)_(3-n)

wherein (X⁵) is a hydrocarbyl having from 1 to about 20 carbon atoms;

wherein (X⁶) is a halide, hydride, or alkoxide; and

wherein “n” is a number from 1 to 3 inclusive;

wherein the fluorided silica-alumina comprises fluoride, silica, andalumina.

In accordance with another embodiment of this invention, a process isprovided comprising contacting at least one monomer and the catalystcomposition under polymerization conditions to produce a polymer.

In accordance with another embodiment of this invention, an article isprovided. The article comprises the polymer produced in accordance withthis invention.

These objects, and other objects, will become more apparent to thosewith ordinary skill in the art after reading this disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

In the drawings, forming a part hereafter,

FIG. 1 discloses a graph of the activity of the catalyst composition atvarious fluoride loadings and calcining temperatures.

FIG. 2 discloses a graph of the activity versus percent NH₄HF₂ added.

DETAILED DESCRIPTION OF THE INVENTION

Organometal compounds used in this invention have the following generalformula:(X¹)(X²)(X³)(X⁴)M¹In this formula, M¹ is selected from the group consisting of titanium,zirconium, and hafnium. Currently, it is most preferred when M¹ iszirconium.

In this formula, (X¹) is independently selected from the groupconsisting of (hereafter “Group OMC-I”) cyclopentadienyls, indenyls,fluorenyls, substituted cyclopentadienyls, substituted indenyls, suchas, for example, tetrahydroindenyls, and substituted fluorenyls, suchas, for example, octahydrofluorenyls.

Substituents on the substituted cyclopentadienyls, substituted indenyls,and substituted fluorenyls of (X¹) can be selected independently fromthe group consisting of aliphatic groups, cyclic groups, combinations ofaliphatic and cyclic groups, silyl groups, alkyl halide groups, halides,organometallic groups, phosphorus groups, nitrogen groups, silicon,phosphorus, boron, germanium, and hydrogen, as long as these groups donot substantially, and adversely, affect the polymerization activity ofthe catalyst composition.

Suitable examples of aliphatic groups are hydrocarbyls such as, forexample, paraffins and olefins. Suitable examples of cyclic groups arecycloparaffins, cycloolefins, cycloacetylenes, and arenes. Substitutedsilyl groups include, but are not limited to, alkylsilyl groups whereeach alkyl group contains from 1 to about 12 carbon atoms, arylsilylgroups, and arylalkylsilyl groups. Suitable alkyl halide groups havealkyl groups with 1 to about 12 carbon atoms. Suitable organometallicgroups include, but are not limited to, substituted silyl derivatives,substituted tin groups, substituted germanium groups, and substitutedboron groups.

Suitable examples of such substituents are methyl, ethyl, propyl, butyl,tert-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl,nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl, phenyl, chloro,bromo, iodo, trimethylsilyl, and phenyloctylsilyl.

In this formula, (X³) and (X⁴) are independently selected from the groupconsisting of (hereafter “Group OMC-II”) halides, aliphatic groups,substituted aliphatic groups, cyclic groups, substituted cyclic groups,combinations of aliphatic groups and cyclic groups, combinations ofsubstituted aliphatic groups and cyclic groups, combinations ofaliphatic groups and substituted cyclic groups, combinations ofsubstituted aliphatic and substituted cyclic groups, amido groups,substituted amido groups, phosphido groups, substituted phosphidogroups, alkyloxide groups, substituted alkyloxide groups, aryloxidegroups, substituted aryloxide groups, organometallic groups, andsubstituted organometallic groups, as long as these groups do notsubstantially, and adversely, affect the polymerization activity of thecatalyst composition.

Suitable examples of aliphatic groups are hydrocarbyls, such as, forexample, paraffins and olefins. Suitable examples of cyclic groups arecycloparaffins, cycloolefins, cycloacetylenes, and arenes. Currently, itis preferred when (X³) and (X⁴) are selected from the group consistingof halides and hydrocarbyls, where such hydrocarbyls have from 1 toabout 10 carbon atoms. However, it is most preferred when (X³) and (X⁴)are selected from the group consisting of fluoro, chloro, and methyl.

In this formula, (X²) can be selected from either Group OMC-I or GroupOMC-II.

At least one substituent on (X¹) or (X²) can be a bridging group thatconnects (X¹) and (X²), as long as the bridging group does notsubstantially, and adversely, affect the activity of the catalystcomposition. Suitable bridging groups include, but are not limited to,aliphatic groups, cyclic groups, combinations of aliphatic groups andcyclic groups, phosphorous groups, nitrogen groups, organometallicgroups, silicon, phosphorus, boron, and germanium.

Suitable examples of aliphatic groups are hydrocarbyls, such as, forexample, paraffins and olefins. Suitable examples of cyclic groups arecycloparaffins, cycloolefins, cycloacetylenes, and arenes. Suitableorganometallic groups include, but are not limited to, substituted silylderivatives, substituted tin groups, substituted germanium groups, andsubstituted boron groups.

Various processes are known to make these organometal compounds. See,for example, U.S. Pat. Nos. 4,939,217; 5,210,352; 5,436,305; 5,401,817;5,631,335, 5,571,880; 5,191,132; 5,480,848; 5,399,636; 5,565,592;5,347,026; 5,594,078; 5,498,581; 5,496,781; 5,563,284; 5,554,795;5,420,320; 5,451,649; 5,541,272; 5,705,478; 5,631,203; 5,654,454;5,705,579; and 5,668,230; the entire disclosures of which are herebyincorporated by reference.

Specific examples of such organometal compounds are as follows:

bis(cyclopentadienyl)hafnium dichloride;

bis(cyclopentadienyl)zirconium dichloride;

1,2-ethanediylbis(η⁵-1-indenyl)di-n-butoxyhafnium;

1,2-ethanediylbis(η⁵-1-indenyl)dimethylzirconium;

3,3-pentanediylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)hafnium dichloride;

methylphenylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride;

bis(n-butylcyclopentadienyl)bis(di-t-butylamido)hafnium;

bis(n-butylcyclopentadienyl)zirconium dichloride;

dimethylsilylbis(1-indenyl)zirconium dichloride;

octylphenylsilylbis(1-indenyl)hafnium dichloride;

dimethylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride;

dimethylsilylbis(2-methyl-1-indenyl)zirconium dichloride;

1,2-ethanediylbis(9-fluorenyl)zirconium dichloride;

indenyl diethoxy titanium(IV) chloride;

(isopropylamidodimethylsilyl)cyclopentadienyltitanium dichloride;

bis(pentamethylcyclopentadienyl)zirconium dichloride;

bis(indenyl) zirconium dichloride;

methyloctylsilyl bis (9-fluorenyl) zirconium dichloride;

bis-[1-(N,N-diisopropylamino)boratabenzene]hydridozirconiumtrifluoromethylsulfonate

Preferably, said organometal compound is selected from the groupconsisting of

bis(n-butylcyclopentadienyl)zirconium dichloride;

bis(indenyl)zirconium dichloride;

dimethylsilylbis(1-indenyl) zirconium dichloride;

methyloctylsilylbis(9-fluorenyl)zirconium dichloride

Organoaluminum compounds have the following general formula:Al(X⁵)_(n)(X⁶)_(3-n)In this formula. (X⁵) is a hydrocarbyl having from 1 to about 20 carbonatoms. Currently, it is preferred when (X⁵) is an alkyl having from 1 toabout 10 carbon atoms. However, it is most preferred when (X⁵) isselected from the group consisting of methyl, ethyl, propyl, butyl, andisobutyl.

In this formula, (X⁶) is a halide, hydride, or alkoxide. Currently, itis preferred when (X⁶) is independently selected from the groupconsisting of fluoro and chloro. However, it is most preferred when (X⁶)is chloro.

In this formula, “n” is a number from 1 to 3 inclusive. However, it ispreferred when “n” is 3.

Examples of such compounds are as follows:

-   -   trimethylaluminum;    -   triethylaluminum (TEA);    -   tripropylaluminum;    -   diethylaluminum ethoxide;    -   tributylaluminum;    -   triisobutylaluminum hydride;    -   triisobutylaluminum; and    -   diethylaluminum chloride.        Currently, TEA is preferred.

The fluorided silica-alumina comprises silica, alumina and fluoride. Thefluorided silica-alumina is in the form of a particulate solid.Generally, to produce the fluorided silica-alumina, a silica-alumina istreated with a fluoriding agent, in order to add fluoride to thesilica-alumina. Generally, the fluoride is added to the silica-aluminaby forming a slurry of the silica-alumina in a solution of thefluoriding agent and a suitable solvent such as alcohol or water.Particularly suitable are one to three carbon atom alcohols because oftheir volatility and low surface tension. A suitable amount of thesolution is utilized to provide the desired concentration of fluoride onthe silica-alumina after drying. Drying can be effected by any methodknown in the art. For example, said drying can be completed by suctionfiltration followed by evaporation, drying under vacuum, or by spraydrying.

Any organic or inorganic fluoriding agent which can form a surfacefluoride with a silica-alumina can be used in this invention. Suitablefluoriding agents include, but are not limited to, hydrofluoric acid(HF), ammonium fluoride (NH₄F), ammonium bifluoride (NH₄HF₂), ammoniumfluoroborate (NH₄BF₄), ammonium silicofluoride ((NH₄)₂SiF₆), ammoniumfluorophosphate (NH₄PF₆), and mixtures thereof The most preferredfluoriding agent is ammonium bifluoride, due to ease of use andavailability. The amount of fluoride present before calcining isgenerally in the range of about 2 to about 50% by weight, preferablyabout 3 to about 25% by weight, and most preferably, 4 to 20% by weight,where the weight percents are based on the weight of the fluoridedsilica-alumina before calcining.

It is important that the fluorided silica-alumina be calcined. Thecalcining can be conducted in any suitable ambient. Generally, thecalcining is conducted in an ambient atmosphere, preferably a dryambient atmosphere, at a temperature in the range of about 200° C. toabout 900° C., and for a time in the range of about 1 minute to about100 hours. Preferably, the fluorided silica-alumina is calcined attemperatures from about 300° C. to about 600° C. and a time in a rangeof about 1 hour to about 10 hours, most preferably, temperatures from350° C. to 550° C. and a time in a range of 1 hours to 10 hours.

Optionally, the silica-alumina can be treated with a fluoriding agentduring calcining. Any fluoriding agent capable of contacting thesilica-alumina during the calcining step can be used. In addition tothose fluoriding agents described previously, organic fluoriding agentsof high volatility are especially useful. Organic fluoriding agents ofhigh volatility can be selected from the group consisting of freons,perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, andmixtures thereof. Gaseous hydrogen fluoride or fluorine itself can beused. One convenient method of contacting the silica-alumina is tovaporize a fluoriding agent into a gas stream used to fluidize thesilica-alumina during calcination.

The silica-alumina should have a pore volume greater than about 0.5cc/g, preferably greater than about 0.8 cc/g, and most preferably,greater than 1.0 cc/g.

The silica-alumina should have a surface area greater than about 100m²/g, preferably greater than about 250 m²/g, and most preferablygreater than 350 m²/g.

The silica-alumina of this invention can have an alumina content fromabout 5 to about 95%, preferably from about 8 to about 50%, and mostpreferably from 10% to 30% alumina by weight.

The catalyst compositions of this invention can be produced bycontacting the organometal compound, the fluorided silica-alumina, andthe organoaluminum compound, together. This contacting can occur in avariety of ways, such as, for example, blending. Furthermore, each ofthese compounds can be fed into a reactor separately, or variouscombinations of these compounds can be contacted together before beingfurther contacted in the reactor, or all three compounds can becontacted together before being introduced into the reactor.

Currently, one method is to first contact an organometal compound and afluorided silica-alumina together, for about 1 minute to about 24 hours,preferably, 1 minute to 1 hour, at a temperature from about 10° C. toabout 200° C., preferably 15° C. to 80° C., to form a first mixture, andthen contact this first mixture with an organoaluminum compound to formthe catalyst composition.

Preferably, the organometal compound, the organoaluminum compound, andthe fluorided silica-alumina are precontacted before injection into thereactor for about 1 minute to about 24 hours, preferably, 1 minute to 1hour, at a temperature from about 10° C. to about 200° C., preferably20° C. to 80° C., in order to obtain high activity.

A weight ratio of organoaluminum compound to the fluoridedsilica-alumina in the catalyst composition ranges from about 5:1 toabout 1:1000, preferably, from about 3:1 to about 1:100, and mostpreferably, from 1:1 to 1:50.

A weight ratio of the fluorided silica-alumina to the organometalcompound in the catalyst composition ranges from about 10,000:1 to about1:1. preferably, from about 1000:1 to about 10:1, and most preferably,from about 250:1 to 20:1. These ratios are based on the amount of thecomponents combined to give the catalyst composition.

After contacting, the catalyst composition comprises a post-contactedorganometal compound, a post-contacted organoaluminum compound, and apost-contacted fluorided silica-alumina. It should be noted that thepost-contacted fluorided silica-alumina is the majority, by weight, ofthe catalyst composition. Often times, specific components of a catalystare not known, therefore, for this invention, the catalyst compositionis described as comprising post-contacted compounds.

The catalyst composition of this invention has an activity greater thana catalyst composition that uses the same organometal compound, and thesame organoaluminum compound, but uses alumina, silica, orsilica-alumina that has not been impregnated with fluoride as shown incontrol examples 3–7. Furthermore, the catalyst composition of thisinvention has an activity greater than a catalyst composition that usesthe same organometal compound, and the same organoaluminum compound, butuses a fluorided silica or a fluorided alumina as shown in controlexamples 9–10. This activity is measured under slurry polymerizationconditions, using isobutane as the diluent, and with a polymerizationtemperature of about 50 to about 150° C., and an ethylene pressure ofabout 400 to about 800 psig. When comparing activities, polymerizationruns should occur at the same polymerization conditions. The reactorshould have substantially no indication of any wall scale, coating orother forms of fouling.

However, it is preferred if the activity is greater than about 1000grams of polymer per gram of fluorided silica-alumina per hour, morepreferably greater than about 2000, even more preferably greater than5000, and most preferably greater than 8,000. This activity is measuredunder slurry polymerization conditions, using isobutane as the diluent,and with a polymerization temperature of 90° C., and an ethylenepressure of 550 psig. The reactor should have substantially noindication of any wall scale, coating or other forms of fouling.

One of the important aspects of this invention is that no aluminoxaneneeds to be used in order to form the catalyst composition. Aluminoxaneis an expensive compound that greatly increases polymer productioncosts. This also means that no water is needed to help form suchaluminoxanes. This is beneficial because water can sometimes kill apolymerization process. Additionally, it should be noted that no boratecompounds need to be used in order to form the catalyst composition. Insummary, this means that the catalyst composition, which isheterogenous, and which can be used for polymerizing monomers ormonomers and one or more comonomers, can be easily and inexpensivelyproduced because of the absence of any aluminoxane compounds or boratecompounds. Additionally, no organochromium compound needs to be added,nor any MgCl₂ needs to be added to form the invention. Althoughaluminoxane, borate compounds, organochromium compounds, or MgCl₂ arenot needed in the preferred embodiments, these compounds can be used inother embodiments of this invention.

In another embodiment of this invention, a process comprising contactingat least one monomer and the catalyst composition to produce at leastone polymer is provided. The term “polymer” as used in this disclosureincludes homopolymers and copolymers. The catalyst composition can beused to polymerize at least one monomer to produce a homopolymer or acopolymer. Usually, homopolymers are comprised of monomer residues,having 2 to about 20 carbon atoms per molecule, preferably 2 to about 10carbon atoms per molecule. Currently, it is preferred when at least onemonomer is selected from the group consisting of ethylene, propylene,1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, and mixtures thereof.

When a homopolymer is desired, it is most preferred to polymerizeethylene or propylene. When a copolymer is desired, the copolymercomprises monomer residues and one or more comonomer residues, eachhaving from about 2 to about 20 carbon atoms per molecule. Suitablecomonomers include, but are not limited to, aliphatic 1-olefins havingfrom 3 to 20 carbon atoms per molecule, such as, for example, propylene,1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and otherolefins and conjugated or nonconjugated diolefins such as 1,3-butadiene,isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, 1,4-pentadiene,1,7-hexadiene, and other such diolefins and mixtures thereof. When acopolymer is desired, it is preferred to polymerize ethylene and atleast one comonomer selected from the group consisting of 1-butene,1-pentene, 1-hexene, 1-octene, and 1-decene. The amount of comonomerintroduced into a reactor zone to produce a copolymer is generally fromabout 0.01 to about 10 weight percent comonomer based on the totalweight of the monomer and comonomer, preferably, about 0.01 to about 5,and most preferably, 0.1 to 4. Alternatively, an amount sufficient togive the above described concentrations, by weight, in the copolymerproduced can be used.

Processes that can polymerize at least one monomer to produce a polymerare known in the art, such as, for example, slurry polymerization, gasphase polymerization, and solution polymerization. It is preferred toperform a slurry polymerization in a loop reaction zone. Suitablediluents used in slurry polymerization are well known in the art andinclude hydrocarbons which are liquid under reaction conditions. Theterm “diluent” as used in this disclosure does not necessarily mean aninert material; it is possible that a diluent can contribute topolymerization. Suitable hydrocarbons include, but are not limited to,cyclohexane, isobutane, n-butane, propane, n-pentane, isopentane,neopentane, and n-hexane. Furthermore, it is most preferred to useisobutane as the diluent in a slurry polymerization. Examples of suchtechnology can be found in U.S. Pat. Nos. 4,424,341; 4,501,885;4,613,484; 4,737,280; and 5,597,892; the entire disclosures of which arehereby incorporated by reference.

The catalyst compositions used in this process produce good qualitypolymer particles without substantially fouling the reactor. When thecatalyst composition is to be used in a loop reactor zone under slurrypolymerization conditions, it is preferred when the particle size of thesolid oxide compound is in the range of about 10 to about 1000 microns,preferably about 25 to about 500 microns, and most preferably, 50 to 200microns, for best control during polymerization.

In a more specific embodiment of this invention, a process is providedto produce a catalyst composition, the process comprising (optionally,“consisting essentially of”, or “consisting of”):

-   -   (1) contacting a silica-alumina with water containing ammonium        bifluoride to produce a fluorided silica-alumina;    -   (2) calcining the fluorided silica-alumina at a temperature        within a range of 350 to 550° C. to produce a calcined        composition having 4 to 20 weight percent fluoride based on the        weight of the fluorided silica-alumina before calcining;    -   (3) combining said calcined composition and        bis(n-butylcyclopentadienyl) zirconium dichloride at a        temperature within the range of 15° C. to 80° C. to produce a        mixture; and    -   (4) after between 1 minute and 1 hour, combining said mixture        and triethylaluminum to produce said catalyst composition.

Hydrogen can be used in this invention in a polymerization process tocontrol polymer molecular weight.

After the polymers are produced, they can be formed into variousarticles, such as, for example, household containers and utensils, filmproducts, drums, fuel tanks, pipes, geomembranes, and liners. Variousprocesses can form these articles. Usually, additives and modifiers areadded to the polymer in order to provide desired effects. It is believedthat by using the invention described herein, articles can be producedat a lower cost, while maintaining most, if not all, of the uniqueproperties of polymers produced with metallocene catalysts.

EXAMPLES Testing Methods

A “Quantachrome Autosorb-6 Nitrogen Pore Size Distribution Instrument”was used to determined surface areas and pore volumes. This instrumentwas acquired from the Quantachrome Corporation, Syosset, N.Y.

Preparation of Oxide Compounds for Control Examples 3–7

Silica was obtained from W. R. Grace, grade 952, having a pore volume of1.6 cubic centimeter per gram (cc/g) and a surface area of about 300square meters per gram (m²/g).

About 10 grams of the silica were placed in a 1.75 inch quartz tubefitted with a sintered quartz disk at the bottom. While the silica wassupported on the disk, dry air was blown up through the disk at thelinear rate of about 1.6 to 1.8 standard cubic feet per hour. Anelectric furnace around the quartz tube was then turned on, and thetemperature was raised at the rate of 400° C. per hour to a temperatureof 600° C. At this temperature, the silica was allowed to fluidize forthree hours in the dry air. Afterward, the silica was collected andstored under dry nitrogen. The silica did not have any exposure to theatmosphere.

Alumina sold as Ketjen grade B alumina from Akzo Nobel was obtainedhaving a pore volume of about 1.78 cc/g and a surface area of about 340m²/g. Alumina samples were prepared by the procedure describedpreviously for the silica except the alumina samples were calcined at400° C. 600° C., and 800° C.

A silica-alumina was obtained from W. R. Grace as MS 13-110 containing13% alumina and 87% silica. The silica-alumina had a pore volume of 1.2cc/g and a surface area of about 400 m²/g. Silica-alumina samples wereprepared as described previously for the silica.

General Description of Polymerizations Runs

Polymerization runs were made in a 2.2 liter steel reactor equipped witha marine stirrer running at 400 revolutions per minute (rpm). Thereactor was surrounded by a steel jacket containing boiling methanolwith a connection to a steel condenser. The boiling point of themethanol was controlled by varying nitrogen pressure applied to thecondenser and jacket, which permitted precise temperature control towithin ±0.5° C., with the help of electronic control instruments.

Unless otherwise stated, first, an oxide compound or fluoridedsilica-alumina was charged under nitrogen to a dry reactor. Next, twomilliliters of a solution containing 0.5 grams ofbis(n-butylcyclopentadienyl) zirconium dichloride per 100 milliliters oftoluene were added by syringe. Then, 1.2 liters of isobutane werecharged to the reactor, and the reactor was then heated up to 90° C. Onemilliliter, or two milliliters, of TEA or ethyl aluminum dichloride(EADC) was added midway during the isobutane addition. Finally, ethylenewas added to the reactor to equal 550 psig, which was maintained duringthe experiment. The stirring was allowed to continue for the specifiedtime, and the activity was noted by recording the flow of ethylene intothe reactor to maintain pressure.

After the allotted time, the ethylene flow was stopped, and the reactorslowly depressurized and opened to recover a granular polymer. In allcases, the reactor was clean with no indication of any wall scale,coating, or other forms of fouling. The polymer was then removed, dried,and weighed.

Examples 1–2 (Controls)

This example demonstrates that an organometal compound added to thereactor with TEA or EADC does not provide any activity.

A polymerization run was made as described previously except no oxidecompound was added. Ethylene was added, but no activity was seen. Afterone hour of stirring, the reactor was depressurized and opened, but ineach case no polymer was found. These results are shown in Table 1.

Examples 3–7 (Controls)

This experiment demonstrates the use of different oxide compounds, anorganometal compound, and TEA.

Each of the oxide compounds described previously was added to thereactor, followed by the organometal compound and TEA solutions as usedin the procedure discussed previously. These runs are shown in Table 1.

Silica produced almost no polymer. Alumina, which is regarded as moreacidic than the silica, produced more polymer, but still the activitywas very low. This was true of all three different activationtemperatures tested. The silica-alumina also exhibited only very lowactivity.

TABLE 1 (Control Runs 1–7) Organo- Type of Oxide aluminum Ex- Oxide Cal-Com- Com- Poly- Run Ac- am- Com- cining pound pound mer Time tiv- plepound (° C.) (g) (ml) (g) (min.) ity* 1 None 0.0000 2 (TEA) 0 61.1 0 2None 0.0000 2 (EADC) 0 28.0 0 3 Silica 600 0.5686 2 (TEA) 0.65 63.0 1 4Alumina 800 0.6948 1 (TEA) 2.7 30.7 8 5 Alimina 600 0.2361 2 (TEA) 6.960.9 29 6 Alumina 400 0.8475 1 (TEA) trace 57.2 0 7 Silica- 600 0.3912 1(TEA) 8.3 40.0 32 Alumina *Activity is in units of grams of polymer/gramof oxide compound charged per hour.

Example 8 (Control and Inventive Runs)

The following catalyst compositions were produced to demonstrate thisinvention at different loadings of ammonium bifluoride and at differentcalcination temperatures.

A small amount of a silica-alumina, sold as MS13-110 by W. R. GraceCompany having a surface area of 400 m²/g and a pore volume of 1.2 cc/g,was impregnated with about twice its weight of water containing ammoniumbifluoride dissolved in it to produce a fluorided silica-alumina. Forexample, fifty grams of the silica-alumina was impregnated with 100milliliters of an aqueous solution containing 5 grams of ammoniumbifluoride for a 10 weight percent loading of ammonium bifluoride. Thisresulted in a wet sand consistency.

The fluorided silica-alumina was then placed in a vacuum oven and driedovernight at 110° C. under half an atmosphere of vacuum. The final stepwas to calcine 10 grams of the fluorided silica-alumina in dryfluidizing air at the required temperature for three hours. Thefluorided silica-alumina was then stored under nitrogen until a smallquantity was charged to the reactor with an organometal compound and TEAas described previously in this disclosure.

These runs are shown in Table 2, and they are plotted graphically inFIG. 1. Table 3 shows the most active run from each loading, regardlessof its calcining temperature plotted against ammonium bifluorideloading. These results are plotted graphically in FIG. 2.

As can be seen from the data in Table 3, excellent catalyst activity wasobserved when the ammonium bifluoride loading was from about 5 to about35% by weight with a calcining temperature of from about 300° C. toabout 600° C.

TABLE 2 NH₄HF₂ Fluorided Poly- Run Ex- Loading Silica- mer TimeCalcining ample (wt. %) Alumina (g) (g) (min) (° C.) Activity* 8-1  50.0293 140 69.0 450 4155 8-2  5 0.0188 117 60.1 600 6213 8-3  5 0.035360 37.0 750 2756 8-4  5 0.2318 203 40.0 850 1312 8-5  3 0.1266 205 45.7800 2126 8-6  10 0.0800 68 28.0 300 1816 8-7  10 0.0248 163 67.7 3505825 8-8  10 0.0251 228 44.5 400 12248 8-9  10 0.0183 175 48.0 400 119548-10 10 0.0779 270 20.0 400 10398 8-11 10 0.0109 165 60.0 450 15138 8-1210 0.0059 109 60.0 450 18475 8-13 10 0.0200 224 60.1 500 11181 8-14 100.0792 179 16.0 500 8485 8-15 10 0.0249 175 60.0 550 7028 8-16 10 0.0897149 18.0 600 5537 8-17 10 0.0346 113 60.2 650 3255 8-18 10 0.0908 14921.0 700 4688 8-19 10 0.2336 288 50.0 750 1478 8-20 10 0.0829 91 32.0800 2057 8-21 10 0.2185 183 55.0 850 916 8-22 22 0.1773 319 30.0 2003598 8-23 22 0.2355 320 9.0 300 9068 8-24 22 0.1456 250 21.0 400 48968-25 22 0.0214 34 45.2 500 2109 8-26 22 0.1715 146 31.0 600 1651 8-27 220.1624 88 22.0 700 1474 8-28 35 0.2944 336 10.0 300 6854 8-29 35 0.0786108 15.0 400 5471 8-30 35 0.0725 160 39.0 450 2410 8-31 35 0.0191 5571.7 450 3395 8-32 35 0.0832 58 20.0 500 2091 8-33 35 0.1021 127 25.0600 2989 8-34 35 0.0715 21 26.0 700 689 8-35 70 0.0175 0 92.3 450 0 8-3670 0.0446 0 40.0 450 0 *Activity is in units of grams of polymer/gram offluorided silica-alumina charged per hour.

TABLE 3 NH₄HF₂ Fluorided Poly- Run Ex- Loading Silica- mer TimeCalcining ample (wt. %) Alumina (g) (g) (min) (° C.) Activity* 7 00.3912 8.3 40.0 600 32 8-5  3 0.1266 205 45.7 800 2126 8-2  5 0.0188 11760.1 600 6213 8-11 10 0.0059 109 60.0 450 18475 8-23 22 0.2355 320 9.0300 9068 8-28 35 0.2944 336 10.0 300 6854 8-35 70 0.0175 0 92.3 450 0*Activity is in units of grams of polymer/gram of fluoridedsilica-alumina charged per hour.

Example 9 (Control)

The procedure of example 8 was repeated, except that instead of asilica-alumina, a silica was used instead.

A grade 952 silica obtained from W. R. Grace was impregnated was 10%ammonium bifluoride as described previously in this disclosure toproduce a fluorided silica. The silica has a surface area of about 300m²/g and a pore volume of about 1.6 cc/g. The fluorided silica was thencalcined at 450° C. for three hours in dry air and tested forpolymerization activity. It exhibited no activity at all.

Example 10 (Control)

The procedure of example 8 was repeated, except that instead ofsilica-alumina, an alumina was used instead.

An alumina called Ketjen grade B obtained from Akzo Nobel wasimpregnated with various loadings of ammonium bifluoride to produce afluorided alumina as described previously. The alumina has a surfacearea of about 400 m²/g and a pore volume of about 1.6 cc/g. Thefluorided alumina samples were then calcined at 450° C. or 500° C. forthree hours in dry air and tested for polymerization activity asdescribed previously in this disclosure. These results are shown inTable 4. The activity of the fluorided alumina samples is considerablybelow the activity shown in the inventive runs using a fluoridedsilica-alumina.

TABLE 4 NH₄HF₂ Fluorided Run Ex- Loading Alumina Polymer Time Calciningample (wt. %) (g) (g) (min) (° C.) Activity* 10-1 10 0.1086 17.6 40.0500 243 10-2 15 0.2563 243.9 60.0 500 952 10-3 25 0.2542 164 55.0 450704 10-4 35 0.0157 37 30.0 500 640 *Activity is in units of grams ofpolymer/gram of fluorided alumina charged per hour.

While this invention has been described in detail for the purpose ofillustration, it is not intended to be limited thereby but is intendedto cover all changes and modifications within the spirit and scopethereof.

1. A catalyst composition comprising: a contact product of at least oneorganometal compound, and at least one organoaluminum compound, and atleast one fluorided silica-alumina, the catalyst composition havingcatalytic activity in the substantial absence of organoborates andaluminoxanes, wherein: the organometal compound has the followinggeneral formula:(X¹)(X²)(X³)(X⁴)M¹ wherein: M¹ is selected from titanium, zirconium, orhafnium; (X¹) is independently selected from cyclopentadienyls,indenyls, fluorenyls, substituted cyclopentadienyls, substitutedindenyls, and substituted fluorenyls; substituents on the substitutedcyclopentadienyls, substituted indenyls, and substituted fluorenyls of(X¹) are selected from aliphatic groups, cyclic groups, combinations ofaliphatic and cyclic groups, silyl groups, alkyl halide groups, halides,organometallic groups, phosphorus groups, nitrogen groups, silicon,phosphorus, boron, or germanium; at least one substituent on (X¹) can bea bridging group which connects (X¹) and (X²); (X³) and (X⁴) areindependently selected from halides, aliphatic groups substitutedaliphatic groups, cyclic groups, substituted cyclic groups, combinationsof aliphatic groups and cyclic groups, combinations of substitutedaliphatic groups and cyclic groups, combinations of aliphatic groups andsubstituted cyclic groups, combinations of substituted aliphatic groupsand substituted cyclic groups, amido groups, substituted amido groups,phosphido groups, substituted pphosphido groups, alkyloxide groups,substituted alkyloxide groups, aryloxide groups, substituted aryloxidegroups, organometallic groups, or substituted organometallic groups;(X²) is selected from cyclopentadienyls, indenyls, fluorenyls,substituted cyclopentadienyls, substituted indenyls, substitutedfluorenyls, halides, aliphatic groups, substituted aliphatic groups,cyclic groups, substituted cyclic groups, combinations of aliphaticgroups and cyclic groups, combinations of substituted aliphatic groupsand cyclic groups, combinations of aliphatic groups and substitutedcyclic groups, combinations of substituted aliphatic groups andsubstituted cyclic groups, amido groups, substituted amido groups,phosphido groups, substituted phosphido groups, alkyloxide groups,substituted alkyloxide groups, aryloxide groups, substituted aryloxidegroups, organometallic groups, or substituted organometallic groups;substituents on (X²) are selected from aliphatic groups, cyclic groups,combinations of aliphatic groups and cyclic groups, silyl groups, alkylhalide groups, halides, organometallic groups, phosphorus groups,nitrogen groups, silicon, phosphorus, boron, or germanium; at least onesubstitutuent on (X²) can be a bridging group which connects (X¹) and(X²); the organoaluminum compound has the general formula:Al(X⁵)_(n)(X⁶)_(3-n) wherein: (X⁵) is a hydrocarbyl having from 1 toabout 20 carbon atoms; (X⁶) is a halide, hydride, or alkoxide; and “n”is a number from 1 to 3 inclusive; and the fluorided silica-aluminacomprises fluoride, silica, and alumina.
 2. The catalyst compositionaccording to claim 1, wherein the catalyst composition has an activitygreater than about 1000 grams of polymer per gram of fluoridedsilica-alumina per hour under slurry polymerization conditions, usingisobutane as a diluent, with a polymerization temperature of 90° C., andan ethylene pressure of 550 psig.
 3. The catalyst composition accordingto claim 1, wherein the catalyst composition has an activity greaterthan about 2000 grams of polymer per gram of fluorided silica-aluminaper hour under slurry polymerization conditions, using isobutane as adiluent, with a polymerization temperature of 90° C., and an ethylenepressure of 550 psig.
 4. The catalyst composition according to claim 1,wherein the catalyst composition has an activity greater than about 5000grams of polymer per gram of fluorided silica-alumina per hour underslurry polymerization conditions, using isobutane as a diluent, with apolymerization temperature of 90° C., and an ethylene pressure of 550psig.
 5. The catalyst composition according to claim 1, wherein thecatalyst composition has an activity greater than about 8000 grams ofpolymer per gram of fluorided silica-alumina per hour under slurrypolymerization conditions, using isobutane as a diluent, with apolymerization temperature of 90° C., and an ethylene pressure of 550psig.
 6. The catalyst composition according to claim 1, wherein thecatalyst composition has a weight ratio of organoaluminum compound tofluorided silica-alumina in a range from about 5:1 to about 1:1000. 7.The catalyst composition according to claim 1, wherein the catalystcomposition has a weight ratio of organoaluminum compound to fluoridedsilica-alumina in a range from 3:1 to 1:100.
 8. The catalyst compositionaccording to claim 1, wherein the catalyst composition has a weightratio of organoaluminum compound to fluorided silica-alumina in a rangefrom 1:1 to about 1:50.
 9. The catalyst composition according to claim1, wherein the catalyst composition has a weight ratio of fluoridedsilica-alumina to organoaluminum compound in a range from about 10,000:1to about 1:1.
 10. The catalyst composition according to claim 1, whereinthe catalyst composition has a weight ratio of fluorided silica-aluminato organoaluminum compound in a range from about 1000:1 to about 10:1.11. The catalyst composition according to claim 1, wherein the catalystcomposition has a weight ratio of fluorided silica-alumina toorganoaluminum compound in a range from about 250:1 to 20:1.
 12. Thecatalyst composition as claimed in claim 1, wherein the at least oneorganometal compound is selected from bis(cyclopentadienyl)hafniumdichloride, bis(cyclopentadienyl)zirconium dichloride, 1,2-ethanediylbis(η⁵-1-indenyl)di-n-butoxyhafnium,1,2-ethanediylbis(η⁵-1-indenyl)dimethylzirconium,3,3-pentanediylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)hafnium dichloride,methylphenylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride, bis(n-butylcyclopentadienyl) bis(di-t-butylamido)hafnium,bis(n-butylcyclopentadienyl)zirconium dichloride,dimethylsilylbis(1-indenyl)zirconium dichloride,octylphenylsilylbis(1-indenyl)hafnium dichloride,dimethylsilylbis(η⁵-4,5,6,7-tetrahydro- 1-indenyl)zirconium dichloride,dimethylsilylbis(2-methyl-1-indenyl)zirconium dichloride,1,2-ethanediylbis(9-fluorenyl)zirconium dichloride, indenyl diethoxytitanium(IV) chloride,(isopropylamidodimethylsilyl)cyclopentadienyltitanium dichloride,bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride, methyloctylsilyl bis (9-fluorenyl) zirconiumdichloride, or bis-[1-(N,N-diisopropylamino)boratabenzene]hydridozirconium trifluoromethylsulfonate.
 13. Thecatalyst composition as claimed in claim 1, wherein the organometalcompound is selected from bis(n-butylcyclopentadienyl)zirconiumdichloride, bis(indenyl)zirconium dichloride,dimethylsilylbis(1-indenyl) zirconium dichloride, or methyloctylsilylbis(9-fluorenyl)zirconium dichloride.
 14. The catalyst composition asclaimed in claim 1, wherein the at least one organoaluminum compound isselected from trimethylaluminum, triethylaluminum, tripropylaluminum,diethylaluminum ethoxide, tributylaluminum, diisobutylaluminum hydride,triisobutylaluminum hydride, triisobutylaluminum, or diethylaluminumchloride.
 15. The catalyst composition as claimed in claim 1, whereinthe at least one organoaluminum compound is triethylaluminum.
 16. Acatalyst composition comprising: a post-contacted organometal compound,a post-contacted organoaluminum compound, and a post-contacted fluoridedsilica-alumina comprising fluoride, silica, and alumina; and thecatalyst composition being substantially free of organoborates andaluminoxanes.
 17. The catalyst composition according to claim 16,wherein the catalyst composition has an activity greater than about 1000grams of polymer per gram of fluorided silica-alumina per hour underslurry polymerization conditions, using isobutane as a diluent, with apolymerization temperature of 90° C., and an ethylene pressure of 550psig.
 18. The catalyst composition according to claim 16, wherein thecatalyst composition has an activity greater than about 2000 grams ofpolymer per gram of fluorided silica-alumina per hour under slurrypolymerization conditions, using isobutane as a diluent, with apolymerization temperature of 90° C., and an ethylene pressure of 550psig.
 19. The catalyst composition according to claim 16, wherein thecatalyst composition has an activity greater than about 5000 grams ofpolymer per gram of fluorided silica-alumina per hour under slurrypolymerization conditions, using isobutane as a diluent, with apolymerization temperature of 90° C., and an ethylene pressure of 550psig.
 20. The catalyst composition according to claim 16, wherein thecatalyst composition has an activity greater than about 8000 grams ofpolymer per gram of fluorided silica-alumina per hour under slurrypolymerization conditions, using isobutane as a diluent, with apolymerization temperature of 90° C., and an ethylene pressure of 550psig.
 21. The catalyst composition according to claim 16, wherein thecatalyst composition has a weight ratio of organoaluminum compound tofluorided silica-alumina in a range from about 5:1 to about 1:1000. 22.The catalyst composition according to claim 16, wherein the catalystcomposition has a weight ratio of organoaluminum compound to fluoridedsilica-alumina in a range from 3:1 to 1:100.
 23. The catalystcomposition according to claim 16, wherein the catalyst composition hasa weight ratio of organoaluminum compound to fluorided silica-alumina ina range from 1:1 to about 1:50.
 24. The catalyst composition accordingto claim 16, wherein the catalyst composition has a weight ratio offluorided silica-alumina to organoaluminum compound in a range fromabout 10,000:1 to about 1:1.
 25. The catalyst composition according toclaim 16, wherein the catalyst composition has a weight ratio offluorided silica-alumina to organoaluminum compound in a range fromabout 1000:1 to about 10:1.
 26. The catalyst composition according toclaim 16, wherein the catalyst composition has a weight ratio offluorided silica-alumina to organoaluminum compound in a range fromabout 250:1 to about 20:1.
 27. The catalyst composition according toclaim 16, wherein the organometal compound, prior to contacting, has thefollowing general formula:(X¹)(X²)(X³)(X⁴)M¹ wherein: M¹ is selected from titanium, zirconium, orhafnium; (X¹) is independently selected from cyclopentadienyls,indenyls, fluorenyls, substituted cyclopentadienyls, substitutedindenyls, and substituted fluorenyls; substituents on the substitutedcyclopentadienyls, substituted indenyls, and substituted fluorenyls of(X¹) are selected from aliphatic groups, cyclic groups, combinations ofaliphatic and cyclic groups, silyl groups, alkyl halide groups, halides,organometallic groups, phosphorus groups, nitrogen groups, silicon,phosphorus, boron, or germanium; at least one substituent on (X¹) can bea bridging group which connects (X¹) and (X²); (X³) and (X⁴) areindependently selected from halides, aliphatic groups substitutedaliphatic groups, cyclic groups, substituted cyclic groups, combinationsof aliphatic groups and cyclic groups, combinations of substitutedaliphatic groups and cyclic groups, combinations of aliphatic groups andsubstituted cyclic groups, combinations of substituted aliphatic groupsand substituted cyclic groups, amido groups, substituted amido groups,phosphido groups, substituted pphosphido groups, alkyloxide groups,substituted alkyloxide groups, aryloxide groups, substituted aryloxidegroups, organometallic groups, or substituted organometallic groups;(X²) is selected from cyclopentadienyls, indenyls, fluorenyls,substituted cyclopentadienyls, substituted indenyls, substitutedfluorenyls, halides, aliphatic groups, substituted aliphatic groups,cyclic groups, substituted cyclic groups, combinations of aliphaticgroups and cyclic groups, combinations of substituted aliphatic groupsand cyclic groups, combinations of aliphatic groups and Substitutedcyclic groups, combinations of substituted aliphatic groups andsubstituted cyclic groups, amido groups, substituted amido groups,phosphido groups, substituted phosphido groups, alkyloxide groups,substituted alkyloxide groups, aryloxide groups, substituted aryloxidegroups, organometallic groups, or substituted organometallic groups;substituents on (X²) are selected from aliphatic groups, cyclic groups,combinations of aliphatic groups and cyclic groups, silyl groups, alkylhalide groups, halides, organometallic groups, phosphorus groups,nitrogen groups, silicon, phosphorus, boron, or germanium; at least onesubstitutuent on (X²) can be a bridging group which connects (X¹) and(X²).
 28. The catalyst composition as claimed in claim 16, wherein theat least one organometal compound is selected frombis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)zirconiumdichloride, 1,2-ethanediylbis (η⁵-1-indenyl)di-n-butoxyhafnium,1,2-ethanediylbis(η⁵-1-indenyl)dimethylzirconium,3,3-pentanediylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)hafnium dichloride,methylphenylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride, bis(n-butylcyclopentadienyl) bis(di-t-butylamido)hafnium,bis(n-butylcyclopentadienyl)zirconium dichloride,dimethylsilylbis(1-indenyl)zirconium dichloride,octylphenylsilylbis(1-indenyl)hafnium dichloride,dimethylsilylbis(η⁵-4,5,6,7-tetrahydro- 1-indenyl)zirconium dichloride,dimethylsilylbis(2-methyl-1-indenyl)zirconium dichloride,1,2-ethanediylbis(9-fluorenyl)zirconium dichloride, indenyl diethoxytitanium(IV) chloride,(isopropylamidodimethylsilyl)cyclopentadienyltitanium dichloride,bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride, methyloctylsilyl bis (9-fluorenyl) zirconiumdichloride, or bis-[1-(N,N-diisopropylamino)boratabenzene]hydridozirconium trifluoromethylsulfonate.
 29. Thecatalyst composition as claimed in claim 16, wherein the organometalcompound is selected from bis(n-butylcyclopentadienyl)zirconiumdichloride, bis(indenyl)zirconium dichloride,dimethylsilylbis(1-indenyl) zirconium dichloride, or methyloctylsilylbis(9-fluorenyl)zirconium dichloride.
 30. The catalyst composition asclaimed in claim 16, wherein the organoaluminum compound, prior tocontacting, has the general formula:Al(X⁵)_(n)(X⁶)_(3-n) wherein: (X⁵) is a hydrocarbyl having from 1 toabout 20 carbon atoms; (X⁶) is a halide, hydride, or alkoxide; and “n”is a number from 1 to 3 inclusive.
 31. The catalyst composition asclaimed in claim 16, wherein the organoaluminum compound, prior tocontacting, is selected from trimethylaluminum, triethylaluminum,tripropylaluminum, diethylaluminum ethoxide, tributylaluminum,diisobutylaluminum hydride, triisobutylaluminum hydride,triisobutylaluminum, or diethylaluminum chloride.
 32. The catalystcomposition as claimed in claim 16, wherein the organoaluminum compound,prior to contacting, is triethylaluminum.